Process of making bis (beta chlorethyl) sulfide



Patented Feb. 1 ,1954 2,669,587

UNITED sures PATENT OFFICE PROCESS OF MAKING BIS (BETA CHLOR- ETHYL) SULFIDE George E. Miller, Edgewood Arsenal, Edgar M. Faber, Baltimore, and Arthur- M.- Reeves, Havre de Grace, Md, assignors to the 'United'states of Americaas represented by the Secretary of War No Drawing. Application June 19, 1937, serial No. 149,233

6 Claims. (Cl. 260--609)- (Granted under Title 35, U. 8. Code (1952),

see. 266) l a The invention described herein may be manunot limitedto the precise details herein set forth factured and used by or for the Government for by wa of illustration, governmental purposes, without the payment to Theoretically, the formation .of his (beta chlorthem of any royalty thereon. ethyl) sulfide from. ethylene and sulfur dichlor- This invention relates to an improved process ide is. the ideal method. However, the strong for the manufacture of bis (beta chlorethyl) sultendency of the sulfur dichloride to chlorinate fide commonly known as mustard gas. the mustard gas had not been overcome prior Mustard gas, which is to our invention. These reactions may be ex- 610E201}, pressed by the following. equations:

5 ClOHiQEi CICHZCQ modem set 5' was used during the World War as a war gas, (31032611! and was manufactured for the German army by women, CICHZCIOH reacting ethylene ch'lorhydrin with sodium sulg S l s S HG] fide, with subsequent treatment with hydro- C chloric acid. Later developments showed that 0101520112 0101120112 mustard gas could be produced by the action of Prior to the present invention, sulfur dichlorethylene upon sulfur monochloride. ide containing one per cent of absorbent char- The Levinstein process for mustard gas manucoal had been treated with dry ethylene. Howfacture consists essentially in bringing together ever, t yield was only b t 50% t rd gas sulfur mono-chloride and V y p ethylene gas which was also very impure. Another method in e p e o cr de mu tard as as a Solvent tried was to spray ethylene with mixtures of sult a temperature ranging from A Sllpfur dichloride and sulfur monochloride into a y of unchanged mono-chloride is constantly globular flask at atmospheric pressure. The musmaintained in the reacting liquid until a sufiit 1 gas th btai d tain d large per- Ciently large batch is built Then the Sulfur centage of S2C'L2 which will gradually chlorinate mono-chloride feed is discontinued and the etht mustard y e fe d cont nued u t l fu th abSOIDtiOII According to the present invention the reaction c as s- During the ac t e charge is meto of sulfur dichloride and ethylene is carried out chanically agitated. under pressure with an excess of ethylene. Due

This Levi ste p o ss is acwmpanied by to the increase in pressure, the concentration deposition o Sulfur in the r to p p lines and of ethylene is increased, with a resultant increase valves. u i serious clogging. Since a rin the rapidity of the reaction and a decrease in tain amount of mustard gas remains with this 35 the chlorination of the mustard gas by unresulfur, the removal of the sulfur i comp i acted sulfur dichloride. It has been found that by ha a ds t t e personnelpressures of the order of to 75 pounds or The principal object of this invention is to upward, per square inch in the reaction chamd p n fi t t u s p s f r th her may be used satisfactorily. In a number of manufacture of his (beta chlorethyl) sulfide in 40 runs, a pressure of about 50 pounds per square quantity production. inch has been used with good results. Gener- Another O ject of this invention is to develop ally the reaction is more rapid and there is less a process for the manufacture of his (beta chlorchlorination of the mustard gas as the pressure ethyl) sulfide in which the difficulties occasioned is raised. by the deposition of sulfur in the pipes and valves In order to get a rapid and intimate mixture of are materially reduced. the S012 and ethylene, the spray method is used Another object of this invention is to develop and preferably the sulfur dichloride is sprayed a process for the manufacture of bis (beta chlorinto an atmosphere of ethylene. One specific ethyl) sulfide from ethylene and sulfur dichloride example of our process is as follows: A lead-lined which eliminates the strong tendency of sulfur reactor is filled with ethylene maintained at a dichloride to chlorinate the mustard gas in the pressure of 50 pounds per square inch. Sulfur reaction chamber. dichloride is sprayed into the reactor and the These and other objects of the invention will resultant mustard gas is withdrawn. be apparent from the following description and By the above method, a yield of about 92% claims, it being understood that the invention is mustard gas having a purity of about may 3 be obtained. The temperature in the reaction chamber is generally from 50 to 80 C.

For quantity production, the reactor will be continuously supplied with ethylene to maintain the pressure thereof, and means will be provided to continuously withdraw the liquefied gas.

The invention herein described is not limited to the precise details herein disclosed, since variations therein may be made by those skilled in the art without exceeding the scope of the appended claims.

We claim:

1. The process of making his (beta chlorethyl) sulfide which comprises intimately con tacting sulfur dichloride and ethylene at a pressure of from about 40 pounds to about 75 pounds per square inch.

2. The process of making bis (beta chlorethyl) sulfide which comprises intimately contacting sulfur dichloride and ethylene by spraying under a pressure of from about 40 pounds to about 75 pounds per square inch.

3. The process of making his (beta chlorethyl) sulfide which comprises maintaining an excess of ethylene under pressure, and introducing therein and intimately contacting therewith sulfur dichloride at pressure of from about 40 pounds to about 75 pounds per square inch.

pounds to about 60 pounds per square inch and spraying sulfur dichloride thereinto.

5. The process of making his (beta chlorethyl) sulfide which comprises spraying sulfur dichloride into ethylene maintained at a pressure of substantially 50 pounds per square inch.

6. The process of making bis (beta chlorethyl) sulfide which comprises spraying sulphur dichloride into ethylene maintained under a pressure of from about 40 pounds to about 75 pounds per square inch, maintaining a reaction temperature of from about 50 C. to about 80 C., continuously supplying additional ethylene to maintain the pressure, and withdrawing the liquefied 4. The process of making his (beta chlorethyl) sulfide which comprises maintaining an excess of ethylene under a pressure of from about 40 bi (beta chlorethyl) sulfide.

GEORGE E. MILLER. EDGAR M. FABER. ARTHUR M. REEVES.

References Cited in the file of this patent FOREIGN PATENTS Number Country Date 142,875 Great Britain June 10, 1920 504,814 France July 17, 1920 OTHER REFERENCES (Copy 

1. THE PROCESS OF MAKING BIS (BETA CHLORETHYL) SULFIDE WHICH COMPRISES INTIMATELY CONTACTING SULFUR DICHLORIDE AND ETHYLENE AT A PRESSURE OF FROM ABOUT 40 POUNDS TO ABOUT 75 POUNDS PER SQUARE INCH. 